An esterification hydrogenation composite catalyst, its preparation method, and its application in the synthesis of bio-based nonylene glycol and nonanol.

Abstract

This invention belongs to the field of catalyst technology, specifically relating to an esterification hydrogenation composite catalyst, its preparation method, and its application in the synthesis of bio-based nonanediol and nonanol. The catalyst provided by this invention includes a C-ZrO2 composite support and an active component supported on the surface and pores of the C-ZrO2 composite support; the active component comprises a metal active component and a metal oxide active component; the metal active component includes Cu; and the metal oxide active component includes CeO. x and / or SnO x The CeO x and SnO x In the range 1 < x < 2; a stable Cu-MO is formed between Cu, metal oxide, and C-ZrO2 support. x (CeO) x / SnO x The catalyst, with its C-ZrO2 interface structure, can be used in the synthesis of bio-based nonadiol and bio-based nonanol, exhibiting high selectivity and conversion rate.

Description

Technical Field

[0001] This invention belongs to the field of catalyst technology, specifically relating to an esterification hydrogenation composite catalyst, its preparation method, and its application in the synthesis of bio-based nonylene glycol and nonanol. Background Technology

[0002] The production and use of petrochemical products are highly dependent on fossil fuels, such as oil and natural gas. This not only consumes limited energy resources but also leads to greenhouse gas emissions, exacerbating global warming. Their raw materials mainly come from non-renewable mineral resources, and the extraction process causes severe environmental damage, including soil erosion and ecosystem destruction. Meanwhile, petrochemical waste is often difficult to degrade, becoming a major source of plastic pollution and continuously impacting marine and terrestrial ecosystems. Therefore, there is an urgent need to develop bio-based products to address these environmental and resource issues. Biomass, as the only renewable organic carbon resource in nature, has advantages such as low price, huge reserves, and a short regeneration cycle. Unlike wind, solar, and electricity, biomass provides renewable energy while also providing substances such as carbon, hydrogen, and oxygen, giving it unique advantages and gradually making it an important source of chemical raw materials.

[0003] Alcohols have wide applications in industries such as coatings, inks, lubricants, polymer materials, and surfactants. Traditional alcohol products are mainly derived from petrochemical raw materials, but their production process involves high carbon emissions, making it difficult to meet increasingly stringent environmental regulations. In contrast, bio-based alcohols, such as bio-based nonanol and 1,9-nonanediol, can not only be synthesized from renewable resources but also possess excellent solubility, lubricity, and reactivity, making them a sustainable alternative to traditional petroleum-based alcohols. However, a single alcohol often struggles to simultaneously achieve multiple properties in specific applications, such as solubility, film-forming properties, lubricity, and polymerization reactivity. Therefore, mixed alcohols based on bio-based nonanol and 1,9-nonanediol exhibit superior application potential in multiple fields due to their unique synergistic effects.

[0004] Mixed alcohols, containing both monohydroxy and dihydroxy structures, exhibit excellent compatibility in both polar and nonpolar systems. They can optimize the solubility of coatings and inks, improve rheological properties, and enhance film uniformity. Furthermore, in lubricating oil and cutting fluid applications, the dihydroxy structure of mixed alcohols can form a protective layer on metal surfaces, improving lubrication performance and wear resistance while reducing frictional losses and extending equipment lifespan. Compared to traditional mineral oil-based lubricants, bio-based mixed alcohols not only have better biodegradability but also reduce environmental pollution, aligning with the development trend of green lubrication technology. In the field of polymer materials, mixed alcohols can serve as functional monomers for polymers such as polyurethanes, polyesters, and polycarbonates, imparting better flexibility, durability, and hydrolysis resistance. Moreover, they exhibit good compatibility in plasticizer applications, effectively improving polymer processing performance while reducing the use of traditional phthalate plasticizers, thus lowering health and environmental risks. In surfactant and detergent formulations, mixed alcohols can be used to prepare nonionic surfactants, improving emulsification, wetting, and detergency properties, and are particularly suitable for environmentally friendly low-foaming detergent formulations. In addition, mixed alcohols also exhibit excellent performance in electronic chemicals. For example, they can be used in photoresist solvent systems to improve uniform coating and can be used as dispersants for conductive pastes to optimize dispersion and improve the conductivity of electronic products.

[0005] CN117623862A discloses a method for preparing 1,9-nonanediol, in which polyazelic anhydride, a carbon-based supported base metal catalyst, and a solvent are added to a reaction vessel, sealed, and hydrogen is introduced to replace the air. The mixture is then heated to carry out a hydrogenation reaction. After the reaction is complete, the mixture is cooled to release hydrogen, and 1,9-nonanediol is obtained by distillation. However, under these reaction conditions, the conversion and yield of 1,9-nonanediol are both very low. Patent CN105001046A discloses a process for synthesizing n-nonanediol from 2-octene: using rhodium dicarbonyl acetylacetone (Rh(acac)(CO)) as the main catalyst, Tribi as the ligand, and toluene or benzene as the solvent, a hydroformylation reaction is carried out under CO / H2 syngas conditions to obtain n-nonaneal and residual liquid; then, using Raney nickel as a catalyst, hydrogenation reduction is carried out by heating to generate n-nonanediol. However, this preparation method still has the following shortcomings: the cost of rhodium-based catalysts is high, which is not conducive to large-scale industrial production; the use of toxic solvents such as toluene or benzene poses potential hazards to operators and the environment, and it is difficult to meet the requirements of current environmental regulations.

[0006] Patents CN107537531A, CN117258798A, CN101590407A, and CN105797734A disclose ester hydrogenation catalyst systems using Cu as the main catalyst and supplemented with metals such as Ni, Mn, Co, Fe, Zn, Cr, Ca, and Ba as co-catalysts, with Al2O3, SiO2, and MgO as the support. However, these catalysts suffer from weak metal-support interfacial interactions, a lack of stable interfacial structures, and the tendency for Cu particles to sinter in the liquid phase. Furthermore, they are primarily suitable for the hydrogenation of esters to synthesize short-chain alcohols (C1-C4). For the synthesis of long-chain alcohols, due to their higher boiling points, high-pressure liquid-phase hydrogenation processes are typically required. Under these conditions, traditional catalysts are prone to carbon deposition, catalyst framework collapse, poor hydrothermal stability, and increased side reactions, leading to a rapid decline in catalyst performance and severely limiting their application in the hydrogenation synthesis of long-chain alcohols. Summary of the Invention

[0007] In view of this, the present invention provides an esterification hydrogenation composite catalyst, its preparation method, and its application in the synthesis of bio-based nonadiol and nonanol. The catalyst provided by the present invention can be used in the hydrogenation synthesis process of long-chain alcohols, and has high selectivity for products and high conversion rate of raw materials.

[0008] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0009] This invention provides an esterification hydrogenation composite catalyst, comprising a C-ZrO2 composite support and an active component supported on the surface and in the pores of the support; the active component comprises a metal active component and a metal oxide active component; the metal active component comprises Cu; and the metal oxide active component comprises CeO. x and / or SnO x The CeO x and SnO x The range of values ​​for x is independent, which is 1 < x < 2.

[0010] Preferably, the mass of the active component is 5 to 50 wt% of the mass of the esterification hydrogenation composite catalyst.

[0011] Preferably, the preparation method of the C-ZrO2 composite support includes the following steps:

[0012] Carbon black and Zr(OH)4 colloid were mixed and then subjected to a first calcination under a protective atmosphere to obtain the C-ZrO2 composite carrier.

[0013] The preparation method of the esterification hydrogenation composite catalyst of the present invention includes the following steps:

[0014] The C-ZrO2 composite support is immersed in a metal salt solution, so that the active component is loaded on the surface and pores of the C-ZrO2 composite support to obtain a metal / support; the metal salt solution includes a solution of a first metal salt and a solution of a second metal salt.

[0015] The first metal salt includes a Cu salt; the second metal salt includes a Ce salt and / or a Sn salt.

[0016] The metal / support is sequentially dried, calcined a second time, and reduced to obtain the esterification hydrogenation composite catalyst; the reduction temperature is 250~400℃, and the holding time is 2~4h.

[0017] Preferably, the impregnation time is 6~24h; the metal ion loading in the metal / carrier is 8~15wt%; the second calcination temperature is 200~400℃, and the second calcination time is 1~3h.

[0018] Preferably, the reduction is carried out in a hydrogen-containing mixed atmosphere, wherein the volume concentration of hydrogen in the mixed atmosphere is 5-20%.

[0019] The present invention also provides the application of the esterification hydrogenation composite catalyst described in the above technical solution or the esterification hydrogenation composite catalyst obtained by the above preparation method in the hydrogenation synthesis of long-chain alcohols.

[0020] This invention also provides a method for preparing bio-based nonadiol and bio-based nonanol, comprising the following steps:

[0021] (1) Oleic acid, oxidant, first catalyst and organic solvent are mixed and subjected to first oxidation reaction to obtain oleic acid ozonide;

[0022] (2) Oleic acid ozonides are subjected to a second oxidation reaction under the condition of a second catalyst to obtain nonanoic acid and azelaic acid;

[0023] (3) The mixture of nonanoic acid and azelaic acid and methanol were subjected to esterification reaction under the condition of a third catalyst to obtain methyl nonanoate and dimethyl azelaate;

[0024] (4) Under the conditions of esterification and hydrogenation composite catalyst, methyl nonanoate and dimethyl azelate are hydrogenated to obtain bio-based nonadiol and bio-based nonanol.

[0025] The esterification hydrogenation composite catalyst is the esterification hydrogenation composite catalyst described in the above technical solution or the esterification hydrogenation composite catalyst obtained by the preparation method described above.

[0026] Preferably, the first catalyst is MnO2; the temperature of the first oxidation reaction is -10~80℃, and the time of the first oxidation reaction is 80~240min.

[0027] Preferably, the temperature of the second oxidation reaction is 50~130℃ and the reaction time is 60~400min.

[0028] The esterification hydrogenation composite catalyst provided by this invention has the following advantages compared with the prior art:

[0029] (1) Metallic Cu acts as the main hydrogenation active center, responsible for the activation of H2; SnO x CeO x As an electronic modulator and interfacial agent, it forms a stable metal-oxide interfacial structure with Cu. This interfacial structure can modulate the electronic structure of the Cu surface, reduce the excessive cleavage activity of CO bonds, and thus effectively suppress the increase of side reactions such as CC cleavage that easily occur during the hydrogenation of long-chain esters. Therefore, the metal-oxide synergistic system of the present invention is more conducive to achieving selective hydrogenation of long-chain esters to corresponding long-chain alcohols.

[0030] (2) SnO x CeO x The species exhibits stabilizing and anti-sintering effects on Cu, making it suitable for high-temperature, high-pressure liquid-phase systems. Under high-pressure liquid-phase hydrogenation conditions, traditional Cu-based catalysts are prone to metal particle migration, agglomeration, and sintering, leading to rapid activity decay. This invention introduces SnO... x CeO x Subsequently, a strong interfacial interaction forms between Cu and the oxide, which can significantly improve the dispersion and structural stability of Cu species and inhibit the migration and sintering of metals in the liquid phase environment. Therefore, the composite catalyst of this invention can maintain a stable metal active site structure under high-pressure liquid-phase hydrogenation conditions, making it more suitable for the continuous or long-cycle preparation of long-chain alcohols.

[0031] (3) Long-chain ester molecules have large molecular size and high diffusion resistance, making them more sensitive to the pore structure and surface properties of the catalyst. The composite catalyst of the present invention has good pore structure stability, which can enhance the interfacial contact efficiency of long-chain ester molecules, reduce mass transfer resistance, and thus increase the effective conversion probability of long-chain esters at active sites. Detailed Implementation

[0032] This invention provides an esterification hydrogenation composite catalyst, comprising a C-ZrO2 composite support and an active component supported on the surface and in the pores of the C-ZrO2 composite support; the active component comprises a metal active component and a metal oxide active component; the metal active component comprises Cu, and the metal oxide active component comprises CeO. x and / or SnO x The CeO x and SnO xThe range of values ​​for x is independent, which is 1 < x < 2.

[0033] In one embodiment of the present invention, the mass of the active component is 5 to 50% of the mass of the esterification hydrogenation composite catalyst.

[0034] In this invention, the support is a C-ZrO2 composite support. ZrO2 possesses excellent hydrothermal and structural stability, while carbon materials exhibit good hydrophobicity and anti-carbon deposition properties. In high-pressure liquid-phase hydrogenation processes, traditional catalysts are prone to poor hydrothermal stability and framework collapse. This invention uses a C-ZrO2 composite support, where ZrO2 ensures the overall mechanical strength and hydrothermal stability of the framework; furthermore, the carbon phase reduces surface polarity, weakening the strong adsorption of heavy organic matter on the support surface, thereby effectively inhibiting carbon deposition and mitigating pore blockage. Therefore, this composite support system significantly improves the long-term stability of the catalyst under high-pressure liquid-phase hydrogenation conditions.

[0035] In this invention, the preparation method of the C-ZrO2 composite support may include the following steps:

[0036] Carbon black and Zr(OH)4 colloid are mixed and then calcined under a protective atmosphere to obtain the C-ZrO2 composite carrier. In this invention, the mass ratio of carbon black to ZrO2 sol can be (0.5~2):1, specifically (0.7~1.5):1.

[0037] In this invention, the carbon black may specifically be one or more of acetylene black, Ketjenblack (EC600JD) and Vulcan XC-72, preferably Vulcan XC-72R.

[0038] In this invention, the preparation of the Zr(OH)4 colloid includes the following steps:

[0039] NaOH solution is added dropwise to a solution containing a zirconium oxide precursor to adjust the pH to 8.5-9.5 (preferably 8.5-9). The resulting Zr(OH)4 colloid is aged at room temperature to obtain a stable Zr(OH)4 colloid. In this invention, the zirconium oxide precursor can be ZrOCl2·8H2O or Zr(NO3)4; the aging time can be 0.5-3 h, specifically 0.5-1.5 h.

[0040] In this invention, the carbon black and ZrO2 sol can be mixed by ultrasonic or high-shear dispersion; the mixing time can be 0.25-1 h; drying is also included before the first calcination; the temperature of the first calcination can be 400-600 ℃, specifically 450-550 ℃, and the holding time can be 2-4 h, specifically 2.5-3.5 h.

[0041] This invention also provides a method for preparing the esterification hydrogenation composite catalyst described in the above technical solution, comprising the following steps:

[0042] The C-ZrO2 composite support is immersed in a metal salt solution, so that the active component is loaded on the surface and pores of the C-ZrO2 composite support to obtain a metal / support; the metal salt solution includes a solution of a first metal salt and a solution of a second metal salt.

[0043] The first metal salt includes a Cu salt; the second metal salt includes a Ce salt and / or a Sn salt.

[0044] The metal / support is sequentially dried, calcined a second time, and reduced to obtain the esterification hydrogenation composite catalyst; the reduction temperature is 250~400℃; and the holding time is 2~4h.

[0045] In this invention, a C-ZrO2 composite support is immersed in a metal salt solution, so that the active component is loaded on the surface and pores of the C-ZrO2 composite support, thereby obtaining a metal / support.

[0046] In this invention, the metal salt solution includes a solution of a first metal salt and a solution of a second metal salt; the first metal salt includes a Cu salt; the second metal salt includes a Ce salt and / or a Sn salt; the first metal salt is a Cu salt, which can be one or more of copper nitrate, copper acetate, and copper chloride; the Sn salt can be tin chloride and / or tin nitrate; and the Ce salt can be cerium nitrate.

[0047] In this invention, the mass ratio of the first metal salt to the second metal salt can be 1:(0.1~2.5).

[0048] In this invention, the loading of metal ions in the metal / carrier can be 8 to 18 wt%, specifically 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, or 18 wt%.

[0049] The present invention involves drying, second calcination and reduction of the metal / support in sequence to obtain the esterification hydrogenation composite catalyst.

[0050] In this invention, the impregnation time can be 6~24 h, specifically 8~15 h; the drying temperature can be 80~120 ℃, and the time can be 6~16 h; the second calcination temperature can be 200~400 ℃, and the second calcination time can be 1~3 h.

[0051] In this invention, the reduction can be carried out in a hydrogen-containing mixed atmosphere, where the volume concentration of hydrogen can be 5-20%, specifically 5%, 10%, or 15%; the reduction temperature can be 250-400℃, specifically 250℃, 300℃, or 400℃, and the holding time can be 2-4 hours, specifically 2 hours, 3 hours, or 4 hours. In this invention, the reduction can enhance the catalytic activity of the catalyst.

[0052] This invention also provides the application of the esterification-hydrogenation composite catalyst described above in the hydrogenation synthesis of long-chain alcohols.

[0053] This invention also provides a method for preparing nonanol and 1,9-nonanediol, comprising the following steps:

[0054] (1) Oleic acid, oxidant, first catalyst and organic solvent are mixed and subjected to first oxidation reaction to obtain oleic acid ozonide;

[0055] (2) Oleic acid ozonides are subjected to a second oxidation reaction under the condition of a second catalyst to obtain nonanoic acid and azelaic acid;

[0056] (3) The mixture of nonanoic acid and azelaic acid and methanol were subjected to esterification reaction under the condition of a third catalyst to obtain methyl nonanoate and dimethyl azelaate;

[0057] (4) Under the conditions of esterification and hydrogenation composite catalyst, methyl nonanoate and dimethyl azelate are hydrogenated to obtain bio-based nonadiol and bio-based nonanol.

[0058] The esterification hydrogenation composite catalyst is the esterification hydrogenation composite catalyst described in the above technical solution or the esterification hydrogenation composite catalyst obtained by the preparation method described above.

[0059] The present invention mixes oleic acid, an oxidant, a first catalyst and an organic solvent to carry out a first oxidation reaction to obtain oleic acid ozonooxide.

[0060] In this invention, the oleic acid is pure oleic acid or crude oleic acid, purchased from the market or obtained in-house. The oleic acid can be obtained from vegetable oils (such as olive oil or soybean oil) through sequential hydrolysis and purification; the purification steps may include: centrifugation to separate glycerol and the aqueous phase, extraction to remove impurities, and refining steps such as vacuum distillation, decolorization, and deodorization. In this invention, the hydrolysis can be enzymatic hydrolysis or acid-catalyzed hydrolysis.

[0061] In this invention, the organic solvent may include one or more of fatty acid, ether, ester, and ketone organic solvents, specifically C4-C8 ether, ester solvents, or C5-C9 monobasic saturated fatty acid solvents. The C4-C8 ether solvent may be di-n-butyl ether and / or isobutyl acetate. The C5-C9 monobasic saturated fatty acid solvent may be one or more of valeric acid, hexanoic acid, heptanoic acid, octanoic acid, and nonanoic acid, specifically hexanoic acid and nonanoic acid. In this invention, the mass-to-volume ratio of oleic acid to the organic solvent may be 1 g : (0.2-5) mL, specifically 1 g : (1-5) mL. In this invention, the oxidant may be ozone; the first catalyst may be MnO2; MnO2, as a catalyst, can enhance the decomposition activity of ozone and increase the reaction rate.

[0062] In this invention, the oleic acid, oxidant, first catalyst and organic solvent can be mixed by stirring, and the stirring speed can be 200~500 rpm, specifically 300 rpm; the temperature of the first oxidation reaction can be -10~80℃, and the time can be 80~240 min.

[0063] This invention involves subjecting oleic acid ozonides to a second oxidation reaction under a second catalyst to obtain nonanoic acid and azelaic acid.

[0064] In this invention, the oxidant in the second oxidation reaction is oxygen; the oxygen flow rate is 10~40 m³. 3 / h, which can be specifically 20 m 3 / h; the second oxidation reaction can be carried out under stirring conditions; the stirring speed can be 300~600 rpm; the second catalyst can be manganese acetate; the mass of the second catalyst is 0.1~5% of the mass of oleic acid. In this invention, the temperature of the second oxidation reaction can be 50~130 ℃, specifically 60~120 ℃, and the time can be 60~400 min.

[0065] In this invention, after the second oxidation reaction, the process preferably further includes distillation and fractionation of the system obtained from the second oxidation reaction. In this invention, distillation removes small amounts of low-carbon dicarboxylic acids from the oxidation product mixture to ensure product purity. Subsequently, a precisely controlled fractionation process effectively separates high-carbon dicarboxylic acids. After this series of operations, a mixture of azelaic acid and nonanoic acid is finally obtained, suitable for further purification or application.

[0066] The present invention involves esterifying a mixture of nonanoic acid and azelaic acid with methanol under a third catalyst to obtain methyl nonanoate and dimethyl azelaate.

[0067] In this invention, the third catalyst can be a resin catalyst; the resin catalyst can be a strong acid cation exchange resin; in this invention, the obtained products are high-value-added methyl nonanoate and dimethyl azelaate, which are widely used in the synthesis of lubricants, plasticizers, coatings, inks, cosmetics and fine chemicals, and have good commercial value.

[0068] This invention describes the hydrogenation reaction of dimethyl azelaate under the conditions of an esterification-hydrogenation composite catalyst to obtain bio-based nonanol and 1,9-nonanediol.

[0069] In this invention, during the hydrogenation reaction, the flow rate of hydrogen gas can be 100~300 mL / min, the temperature of the hydrogenation reaction can be 170~220 ℃, the pressure of the reaction can be 2.0~15.0 MPa, and the flow rate of the materials (methyl nonanoate and dimethyl azelaate) can be 0.10~1.0 mL / min.

[0070] Compared with the prior art, the preparation method of the present invention has the following advantages:

[0071] (1) The ozonation reaction of oleic acid in this invention uses a non-aqueous mixed solvent system. The mixed solvent has high solubility and low viscosity, which effectively enhances the solubility of ozone and oleic acid in the system and reduces the overall viscosity. In addition, ozone has excellent solubility and good stability in the mixed solvent and is not prone to decomposition reactions to generate aldehydes and ketones. This design helps to promote the transfer and diffusion of heat, which helps to promote the ozonation of double bonds in oleic acid, thereby improving the speed and efficiency of the ozonation reaction, while ensuring the safety of the reaction process.

[0072] (2) This invention utilizes MnO2 as a co-catalyst to significantly improve the reaction rate and optimize product selectivity. MnO2 catalyzes the decomposition of ozone, generating more reactive oxygen species, thereby accelerating the oxidation reaction of oleic acid and reducing the formation of byproducts. Compared with traditional ozonation methods, this invention can be carried out efficiently under mild conditions, reducing energy consumption, and is applicable to aqueous, two-phase, or pure organic phase systems. In addition, MnO2 has good stability and can be recycled through loading or recovery, improving catalyst utilization and reducing production costs. This invention improves ozone oxidation efficiency through the co-catalytic effect of MnO2, achieving higher conversion rates and target product purity, thereby enhancing the industrial application value of oleic acid ozonation technology.

[0073] (3) A mixture of nonanoic acid and azelaic acid is reacted with methanol to obtain methyl nonanoate and dimethyl azelaate. After the reaction is completed, no complicated post-processing steps are required. The products, methyl nonanoate and dimethyl azelaate, can be directly introduced into the hydrogenation reduction process without distillation purification. This not only simplifies the preparation steps but also effectively reduces production time and production costs, and improves the preparation efficiency and production economy of the process.

[0074] (4) The composite catalyst Cu-MO provided by the present invention x (CeO) x and / or SnO x ) / -C-ZrO2 exhibits excellent performance in the esterification and hydrogenation synthesis of long-chain diols. Copper in this catalyst possesses good hydrogenation activity, and MO... x The introduction of [a specific catalyst] can modulate the electronic structure of copper, making the copper surface more susceptible to adsorption of ester groups, while suppressing excessive hydrogenation and side reactions, thus improving the selectivity and yield of the target diol. The C-ZrO2 composite support combines the excellent electronic conductivity of carbon black with the excellent structural stability of zirconium oxide, effectively dispersing the active components and significantly improving the catalyst's thermal stability and anti-sintering properties, extending its lifespan. Compared to traditional Cu-Zn-Al catalysts, the catalyst of this invention can effectively suppress carbon deposition, catalyst collapse, and deactivation, adapt to high-pressure liquid-phase hydrogenation conditions, and has significant advantages such as high reaction rate, fewer side reactions, and good cycle stability. It is particularly suitable for the efficient conversion of long-chain aliphatic ester feedstocks such as oleic acid esters.

[0075] (5) An efficient and environmentally friendly preparation process using biomass feedstocks has been developed for the production of bio-based nonanol and 1,9-nonanediol. This method reduces dependence on fossil fuels, lowers greenhouse gas emissions, and avoids the environmental damage caused by petrochemical production. In addition, biomass feedstocks are renewable, low-cost, and have short production cycles, making the production process more economical and sustainable, and helping to reduce plastic pollution and improve resource utilization efficiency.

[0076] (6) This process has high conversion rate and selectivity, and bio-based nonanol and bio-based nonadiol can be widely used in bio-based solvents, lubricants, and other green chemistry fields. The advantage of this process is that it utilizes renewable resources (such as oleic acid) and combines them with efficient hydrogenation technology, which significantly reduces dependence on traditional petrochemical resources while optimizing the purity and performance of the products. The preparation method provided by this invention has high prospects for industrial application and competitive advantages.

[0077] To further illustrate the present invention, the technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0078] Example 1

[0079] (1) Preparation of Zr(OH)4 colloid: Dissolve 58 g ZrOCl2·8H2O in 300 mL of deionized water to obtain zirconium-containing precursor solution; add 1 M NaOH solution to the solution until pH is 9 to generate white Zr(OH)4 colloid. Age at room temperature for 1 h to make the colloidal particles uniformly dispersed and obtain stable Zr(OH)4 colloid, which can be directly used for subsequent composite carrier preparation.

[0080] (2) Preparation of C-ZrO2 composite support: 22 g of carbon black and 22 g of Zr(OH)4 colloid were mixed, ultrasonically dispersed for 30 min, and dried at 80 ℃ for 12 h. After drying, the mixture was calcined at 500 ℃ for 3 h under a nitrogen atmosphere to obtain the C-ZrO2 composite support.

[0081] (3) Metal loading: 17.5 g Cu(NO3)2·3H2O and 8.2 g SnCl2·2H2O were dissolved in deionized water to obtain a metal mixed solution; the C-ZrO2 composite support was immersed in the metal mixed solution for 12 h and then dried under reduced pressure to obtain metal / support with a total metal loading of 12 wt%.

[0082] (4) Drying and calcination: The metal / carrier was dried at 100 °C for 12 h and then calcined at 300 °C for 2 h in air atmosphere to obtain the calcined metal / carrier;

[0083] (5) Reduction treatment: The calcined metal / support was placed in a 10 vol.% H2 / N2 atmosphere and reduced at 300 °C for 3 h, then cooled to obtain Cu-SnO. x / C-ZrO2 catalyst (1 < x < 2).

[0084] Example 2

[0085] (1) Preparation of ZrO2 sol: 58 g ZrOCl2·8H2O was dissolved in 300 mL of deionized water to obtain a zirconium-containing precursor solution; 1 M NaOH solution was added dropwise to the solution until the pH was 9 to generate white Zr(OH)4 colloid. The colloid was aged at room temperature for 1 h to make the colloidal particles uniformly dispersed and obtain a stable Zr(OH)4 colloid, which can be directly used for subsequent composite carrier preparation.

[0086] (2) Preparation of C-ZrO2 composite support: 22 g of carbon black and 22 g of Zr(OH)4 colloid were mixed, ultrasonically dispersed for 30 min, and dried at 80 ℃ for 12 h. After drying, the mixture was calcined at 500 ℃ for 3 h under a nitrogen atmosphere to obtain C-ZrO2 composite support.

[0087] (3) Metal loading: 17.5 g Cu(NO3)2·3H2O and 10.9 g Ce(NO3)3·6H2O were dissolved in water to obtain a metal mixed solution. The C-ZrO2 composite support was immersed in the metal mixed solution for 12 h and then dried under reduced pressure to obtain metal / support. The total metal loading was 18 wt%.

[0088] (4) Drying and calcination: The metal / carrier was dried at 100 °C for 12 h and then calcined at 400 °C for 2 h in air atmosphere to obtain the calcined metal / carrier;

[0089] (5) Reduction treatment: The calcined metal / support was placed in a 10 vol.% H2 / N2 atmosphere at 300 °C for 3 h for reduction, and then cooled to obtain Cu-CeO. x / C-ZrO2 catalyst.

[0090] Comparative Example 1

[0091] (1) Preparation of ZrO2 sol: Dissolve 58 g ZrOCl2·8H2O in 300 mL of deionized water, and add 1M NaOH solution dropwise while stirring until pH=9. Let the resulting white precipitate stand for 1 h to age, so that the colloidal particles are evenly dispersed, and obtain Zr(OH)4 colloidal solution.

[0092] (2) Preparation of C-ZrO2 composite support: 20 g of carbon black and 20 g of Zr(OH)4 colloid were mixed and ultrasonically dispersed for 30 min, and then dried at 80 ℃ for 12 h. After drying, the mixture was calcined at 500 ℃ for 3 h in nitrogen to obtain C-ZrO2 composite support.

[0093] (3) Metal loading: 17.5 g Cu(NO3)2·3H2O and 8.9 g Zn(NO3)2·6H2O were dissolved in deionized water to form a metal mixed solution. Then, the C-ZrO2 support was immersed in the metal mixed solution for 12 h and then dried under reduced pressure to obtain metal / support with a total metal loading of 15 wt%.

[0094] (4) Drying and calcination: The metal / carrier was dried at 100 °C for 12 h and then calcined in air at 350 °C for 2 h to obtain the calcined composite carrier.

[0095] (5) Reduction treatment: The calcined metal / support was placed in a 10 vol.% H2 / N2 mixed gas and reduced at 300 °C for 3 h. After cooling, Cu-ZnO / C-ZrO2 catalyst was obtained.

[0096] Comparative Example 2

[0097] (1) Preparation of C-Al2O3 support: 30 g of activated carbon and 30 g of γ-Al2O3 powder were added to 200 mL of deionized water and stirred for 1 h. After ultrasonic dispersion for 20 min, the mixture was dried at 100 °C for 12 h and then calcined at 500 °C for 2 h under nitrogen atmosphere to obtain C-Al2O3 composite support.

[0098] (2) Metal loading: 17.5 g Cu(NO3)2·3H2O and 13.5 g Fe(NO3)3·9H2O were dissolved in deionized water to prepare a metal mixed solution. The carrier was added to the metal mixed solution and immersed for 10 h. Then, it was dried under reduced pressure to obtain metal / carrier with a total metal loading of 8 wt%.

[0099] (3) Drying and calcination: The metal / carrier was dried at 110 °C for 10 h and calcined in air at 350 °C for 3 h to obtain the calcined metal / carrier.

[0100] (4) Reduction treatment: The calcined metal / support was placed in a 10 vol.% H2 / N2 mixed gas and reduced at 320 °C for 4 h. After cooling, Cu-Fe2O3 / C-Al2O3 catalyst was obtained.

[0101] Comparative Example 3

[0102] (1) Carrier preparation: Select 40g of activated carbon with a particle size of 100~200 mesh, dry and dehumidify at 80℃ and set aside.

[0103] (2) Metal impregnation: 17.5 g Cu(NO3)2·3H2O and 4.1 g SnCl2·2H2O were dissolved in deionized water to obtain a metal mixed solution; activated carbon was added to the metal mixed solution and stirred for 6 h, and then allowed to stand for 12 h for impregnation and adsorption. Subsequently, the solution was dried under reduced pressure to obtain metal / carrier with a total metal loading of 10 wt%.

[0104] (3) Drying and calcination: The metal / carrier was dried at 100 °C for 12 h and calcined at 300 °C for 2 h in air atmosphere to obtain the calcined metal / carrier.

[0105] (4) Reduction treatment: The calcined metal / support was reduced at 280 °C for 3 h in a 10 vol.% H2 / N2 atmosphere, and then cooled to obtain Cu-SnO. x / C catalyst (1 < x < 2).

[0106] Comparative Example 4

[0107] The preparation method of Cu-Zn-Al esterification hydrogenation catalyst is as follows:

[0108] (1) Solution preparation

[0109] According to the molar ratio Cu:Zn:Al=65:15:10, 8.92 g Cu(NO3)2·3H2O, 8.91 g Zn(NO3)2·6H2O, and 5.03 g Al(NO3)3·9H2O were dissolved in 500 mL of deionized water and stirred until completely dissolved to obtain a mixed metal solution with a total metal ion concentration of about 1 mol / L.

[0110] (2) Coprecipitation preparation of catalyst precursor

[0111] Prepare 300 mL of 1.5 mol / L sodium hydroxide solution as the precipitant solution. Under magnetic stirring (600 rpm), add the metal mixture solution dropwise to the precipitant solution at a flow rate of 10 mL / min, while maintaining pH=8 (adjusted using dilute nitric acid or NaOH). Continue stirring the precipitate for 2 h to complete the co-precipitation process and form the catalyst precursor precipitate.

[0112] (3) Aging, filtration and drying

[0113] The precipitate was aged at 60 °C for 6 h. Vacuum filtration was performed, and the precipitate was washed with deionized water until the pH of the washing solution was approximately 7. The precipitate was then dried at 110 °C for 10 h to obtain the dried catalyst precursor.

[0114] (4) Calcination treatment

[0115] In a muffle furnace, the dried catalyst precursor was placed in an air atmosphere and heated to 500 °C at a heating rate of 5 °C / min, and held for 4 h to obtain the calcined catalyst precursor.

[0116] (5) Reduction activation

[0117] The calcined catalyst precursor is placed in a tubular furnace or fixed-bed reactor, and 10% H2 / N2 gas is introduced. The temperature is increased to 350 °C at 3 °C / min and maintained for 6 h for reduction to obtain Cu-Zn-Al catalyst.

[0118] Application Example 1

[0119] (1) Oleic acid ozonolysis reaction

[0120] 100 g of oleic acid was dissolved in 300 mL of a mixed solvent of hexanoic acid and nonanoic acid, with a volume ratio of hexanoic acid to nonanoic acid of 1:4. 1 g of MnO2 was added to the solution, and the solution was stirred at a constant temperature of 25 °C at a speed of 300 rpm. Under these conditions, ozone was introduced to carry out an ozonolysis reaction at 10 °C for 120 min, yielding oleic acid ozonides.

[0121] (2) Oxidation reaction

[0122] The oleic acid ozonides obtained above were added to a 500 mL oxidation reactor, along with 5 g of manganese acetate as a catalyst. The reaction temperature was controlled at 100 °C. Oxygen was introduced into the reactor at a flow rate of 20 m³ / min. 3 The stirring rate was set to 400 rpm. The reaction was carried out for 120 min, yielding a mixture of crude nonanoic acid and azelaic acid. The crude product was transferred to a distillation apparatus. First, the mixture was distilled to remove low-carbon dicarboxylic acid impurities (adipic acid), with the separation temperature precisely controlled (230 °C) to obtain the target product with high purity. Then, under precisely controlled fractionation conditions (3 kPa, column top temperature 195 °C, and reboiler temperature controlled at 250 °C), the high-carbon dicarboxylic acid was further separated to obtain a mixture of the main products, nonanoic acid and azelaic acid.

[0123] (3) Esterification reaction

[0124] A mixture of 100 g of nonanoic acid and azelaic acid, 100 mL of methanol, and 10 g of a strong acid cation exchange resin were successively added to a reactor. The mixture was heated to 50 °C for pre-esterification. After the solid acid in the reactor was completely dissolved, the mixture was stirred, and 300 mL of methanol was slowly added. The reaction temperature was 70 °C for 15 h, yielding a mixture of methyl nonanoate and dimethyl azelaate. After the reaction, the strong acid cation exchange resin was removed by filtration, yielding the esterification product.

[0125] (4) Hydrogenation reduction reaction

[0126] The obtained dimethyl azelate was transferred to the feed tank of a fixed-bed hydrogenation reactor, and 10 g of Cu-SnO prepared in Example 1 was used. x Hydrogenation was carried out using a C-ZrO2 catalyst. The hydrogen flow rate was set at 200 mL / min, the reaction temperature was maintained at 215 °C, the pressure was set at 10 MPa, and the feed flow rate was set at 0.30 mL / min, producing methanol, bio-based nonanol, and 1,9-nonanediol. The resulting products were analyzed by gas chromatography, showing a feed conversion rate of 99.0% and a target product selectivity of 99.5%.

[0127] Application Example 2

[0128] 100 g of oleic acid was dissolved in 300 mL of valeric acid. 0.1 g of MnO2 was added to the solution, and the mixture was stirred at a constant temperature of 25°C with a stirring speed of 200 rpm. Under these conditions, ozone was introduced to carry out an ozonation reaction for 90 min at a temperature of -10°C, producing oleic acid ozonides.

[0129] The oleic acid ozonides obtained above were added to a 500 mL oxidation reactor, along with 4 g of manganese acetate as a catalyst. The reaction temperature was controlled at 60 °C. Oxygen was introduced into the reactor at a flow rate of 10 m³ / min. 3 The stirring speed was set to 300 rpm. The reaction was continued for 60 min to obtain a mixture of crude nonanoic acid and azelaic acid.

[0130] A mixture of 100 g of nonanoic acid and azelaic acid was reacted with 400 mL of methanol. After the acid was completely dissolved, another 300 mL of methanol was added to obtain a reaction mixture of 700 mL of methanol in total. 5 g of a strongly acidic cation exchange resin was then added to initiate the reaction at 90 °C for 10 h, producing a mixture of methyl nonanoate and dimethyl azelaate.

[0131] The resulting mixture of methyl nonanoate and dimethyl azelate was transferred to the feed tank of a fixed-bed hydrogenation reactor, using 20 g of Cu-SnO prepared in Example 1. x Hydrogenation was carried out using a C-ZrO2 catalyst at a hydrogen flow rate of 220 mL / min, a reaction temperature of 165 °C, a pressure of 3 MPa, and a feed flow rate of 0.30 mL / min for 2 h, yielding bio-based nonanol and 1,9-nonanediol. Gas chromatography analysis of the obtained products showed a conversion rate of 85% and a selectivity of 80% for the target product. Other reaction conditions were the same as in Application Example 1.

[0132] Application Example 3

[0133] 100 g of oleic acid was dissolved in 300 mL of hexanoic acid. 0.5 g of MnO2 was added to the solution, and the mixture was stirred at a constant temperature of 25°C with a stirring speed of 350 rpm. Under these conditions, ozone was introduced to carry out an ozonation reaction. The reaction time was set to 180 min, and the reaction temperature was 20°C, producing oleic acid ozonides.

[0134] The oleic acid ozonides obtained above were added to a 500 mL oxidation reactor, along with 2 g of manganese acetate as a catalyst. The reaction temperature was controlled at 80 °C. Oxygen was introduced into the reactor at a flow rate of 15 m³ / min. 3 The stirring speed was set to 350 rpm. The reaction was continued for 150 min to obtain a mixture of crude nonanoic acid and azelaic acid.

[0135] A mixture of nonanoic acid and azelaic acid was mixed with 400 mL of methanol (300 mL was added after the solid acid was completely dissolved), and 15 g of strong acid cation exchange resin was added to carry out the reaction. The temperature was set at 120 °C and the reaction time was 20 h to produce a mixture of methyl nonanoate and dimethyl azelaate.

[0136] The resulting mixture of methyl nonanoate and dimethyl azelate was transferred to the feed tank of a fixed-bed hydrogenation reactor, using 1 g of Cu-SnO prepared in Example 1. x Hydrogenation was carried out using a C-ZrO2 catalyst. The hydrogen flow rate was set at 240 mL / min, the reaction temperature was maintained at 185 °C, the pressure was set at 5 MPa, the feed flow rate was set at 0.30 mL / min, and the hydrogenation reaction lasted for 4 h, producing bio-based nonanol and 1,9-nonanediol. Gas chromatography analysis of the obtained products showed a conversion rate of 74% and a selectivity of 65% for the target product. Other reaction conditions were the same as in Application Example 1.

[0137] Application Example 4

[0138] 100 g of oleic acid was dissolved in 300 mL of nonanoic acid. 1.5 g of MnO2 was added to the solution, and the mixture was stirred at a constant temperature of 25 °C with the stirring speed adjusted to 400 rpm. Under these conditions, ozone was introduced to carry out an ozonation reaction. The reaction time was set to 240 min, and the reaction temperature was 40 °C, producing oleic acid ozonates.

[0139] The oleic acid ozonides obtained above were added to a 500 mL oxidation reactor, along with 1 g of manganese acetate as a catalyst. The reaction temperature was controlled at 120 °C. Oxygen was introduced into the reactor at a flow rate of 25 m³ / h. 3 The stirring speed was set to 450 rpm. The reaction was continued for 200 min to obtain a mixture of crude nonanoic acid and azelaic acid.

[0140] A mixture of nonanoic acid and azelaic acid was mixed with 400 mL of methanol (300 mL was added after the solid acid was completely dissolved), and 10 g of concentrated sulfuric acid catalyst was added. The temperature was set to 100 °C, and the reaction time was 15 h to produce a mixture of methyl nonanoate and dimethyl azelaate.

[0141] The resulting mixture of methyl nonanoate and dimethyl azelate was transferred to the feed tank of a fixed-bed hydrogenation reactor, using 0.5 g of Cu-SnO prepared in Example 1. x Hydrogenation was carried out using a C-ZrO2 catalyst. The hydrogen flow rate was set at 260 mL / min, the reaction temperature was maintained at 195 °C, the pressure was set at 8 MPa, the feed flow rate was set at 0.30 mL / min, and the hydrogenation reaction lasted for 6 h, producing bio-based nonanol and 1,9-nonanediol. Gas chromatography analysis of the obtained products showed a conversion rate of 68% and a selectivity of 62% for the target product. Other reaction conditions were the same as in Application Example 1.

[0142] Application Example 5

[0143] 100 g of oleic acid was dissolved in 300 mL of octanoic acid. 2 g of MnO2 was added to the solution, and the mixture was stirred at a constant temperature of 25 °C with a stirring speed of 450 rpm. Under these conditions, ozone was introduced to carry out an ozonation reaction. The reaction time was set to 150 min, and the reaction temperature was 60 °C, producing oleic acid ozonides.

[0144] The oleic acid ozonides obtained above were added to a 500 mL oxidation reactor, along with 0.5 g of manganese acetate as a catalyst. The reaction temperature was controlled at 130 °C. Oxygen was introduced into the reactor at a flow rate of 30 m³ / min. 3 The stirring speed was set to 500 rpm. The reaction was continued for 300 min to obtain a mixture of crude nonanoic acid and azelaic acid.

[0145] A mixture of nonanoic acid and azelaic acid was mixed with 400 mL of methanol (300 mL was added after the solid acid was completely dissolved), and 10 g of p-toluenesulfonic acid catalyst was added. The temperature was set to 105 °C, and the reaction time was 15 h to produce a mixture of methyl nonanoate and dimethyl azelaate.

[0146] The resulting mixture of methyl nonanoate and dimethyl azelate was transferred to the feed tank of a fixed-bed hydrogenation reactor, using 0.1 g of Cu-SnO prepared in Example 1. x Hydrogenation was carried out using a C-ZrO2 catalyst. The hydrogen flow rate was set at 280 mL / min, the reaction temperature was maintained at 205 °C, the pressure was set at 12 MPa, the feed flow rate was set at 0.30 mL / min, and the hydrogenation reaction lasted for 8 h, producing bio-based nonanol and 1,9-nonanediol. Gas chromatography analysis of the obtained products showed a conversion rate of 59% and a selectivity of 58% for the target product. Other reaction conditions were the same as in Application Example 1.

[0147] Application Example 6

[0148] The Cu-SnOx / C-ZrO2 catalyst in Application Example 1 was replaced with the Cu-CeO2 catalyst in Example 2. x The C-ZrO2 catalyst was used, and other reaction conditions were the same as in Application Example 1. The resulting product was analyzed by gas chromatography, and the conversion rate of the raw material was 99.3%, and the selectivity of the target product was 99.4%.

[0149] Comparative Application Example 1

[0150] 100 g of oleic acid was dissolved in 300 mL of valeric acid and nonanoic acid, with a volume ratio of valeric acid to nonanoic acid of 1:4. The solution was stirred at a constant temperature of 25 °C with the stirring speed adjusted to 500 rpm. Under these conditions, ozone was introduced to carry out an ozonolysis reaction, with the reaction time set at 200 min and the reaction temperature at 80 °C, producing oleic acid ozonides.

[0151] The oleic acid ozonides obtained above were added to a 500 mL oxidation reactor, along with 0.1 g of manganese acetate as a catalyst. The reaction temperature was controlled at 90 °C. Oxygen was introduced into the reactor at a flow rate of 40 m³ / min. 3 The stirring speed was set to 600 rpm. The reaction was continued for 400 min to obtain a mixture of crude nonanoic acid and azelaic acid.

[0152] A mixture of nonanoic acid and azelaic acid was mixed with 400 mL of methanol (300 mL was added after the solid acid was completely dissolved), and 10 g of sulfate catalyst was added. The temperature was set to 70 °C, and the reaction time was 15 h to produce a mixture of methyl nonanoate and dimethyl azelaate.

[0153] The resulting mixture of methyl nonanoate and dimethyl azelaate was transferred to the feed tank of a fixed-bed hydrogenation reactor, and hydrogenation was performed using 10 g of the Cu-Zn-Al catalyst prepared in Comparative Example 4. The hydrogen flow rate was set to 300 mL / min, the reaction temperature was maintained at 215 °C, the pressure was set to 15 MPa, the feed flow rate was set to 0.30 mL / min, and the hydrogenation reaction lasted for 10 h, producing bio-based nonanol and 1,9-nonanediol. Gas chromatography analysis of the obtained products showed a conversion rate of 42% and a target product selectivity of 48%. Other reaction conditions were the same as in Application Example 1.

[0154] Comparative Application Example 2

[0155] Apply Cu-SnO in Example 1 x The / C-ZrO2 catalyst was replaced with the Cu-ZnO / C-ZrO2 catalyst in Comparative Example 1, and other reaction conditions were the same as in Application Example 1. The resulting product was analyzed by gas chromatography, and the conversion rate of the raw material was 84.2% and the selectivity of the target product was 89.7%.

[0156] Comparative Application Example 3

[0157] Apply Cu-SnO in Example 1 x The / C-ZrO2 catalyst was replaced with the Cu-Fe2O3 / C-Al2O3 catalyst in Comparative Example 2, and other reaction conditions were the same as in Application Example 1. The resulting product was analyzed by gas chromatography, and the conversion rate of the raw material was 72.6%, and the selectivity of the target product was 69.2%.

[0158] Comparative Application Example 4

[0159] Apply Cu-SnO in Example 1 x / The C-ZrO2 catalyst was replaced with Cu-SnO from Comparative Example 3 xWith the catalyst C, other reaction conditions were the same as in Application Example 1. The resulting product was analyzed by gas chromatography, and the feed conversion rate was 78.3%, and the selectivity of the target product was 75.2%.

[0160] Although the above embodiments have provided a detailed description of the present invention, they are only some embodiments of the present invention, and not all embodiments. People can obtain other embodiments based on these embodiments without creative effort, and these embodiments all fall within the protection scope of the present invention.

Claims

1. An esterification-hydrogenation composite catalyst for the synthesis of long-chain alcohols, characterized in that, The composite material includes a C-ZrO2 composite support and active components supported on the surface and in the pores of the C-ZrO2 composite support; the active components include a metal active component and a metal oxide active component; the metal active component includes Cu; the metal oxide active component includes CeO. x and / or SnO x The CeO x and SnO x The range of values ​​for x in the equation is independent, being 1 < x < 2; The preparation method of the C-ZrO2 composite support includes the following steps: Carbon black and Zr(OH)4 colloid were mixed and then subjected to a first calcination under a protective atmosphere to obtain the C-ZrO2 composite carrier.

2. The esterification-hydrogenation composite catalyst as described in claim 1, characterized in that, The mass of the active component is 5-50% of the mass of the esterification hydrogenation composite catalyst.

3. The method for preparing the esterification hydrogenation composite catalyst according to claim 1 or 2, characterized in that, Includes the following steps: The C-ZrO2 composite support is immersed in a metal salt solution, so that the active component is loaded on the surface and pores of the C-ZrO2 composite support to obtain a metal / support; the metal salt solution includes a solution of a first metal salt and a solution of a second metal salt. The first metal salt includes a Cu salt; the second metal salt includes a Ce salt and / or a Sn salt; The metal / support is sequentially dried, calcined a second time, and reduced to obtain the esterification hydrogenation composite catalyst; the reduction temperature is 250~400℃, and the holding time is 2~4h.

4. The preparation method according to claim 3, characterized in that, The impregnation time is 6~24h; the metal ion loading in the metal / carrier is 8~18wt%; the second calcination temperature is 200~400℃, and the second calcination time is 1~3h.

5. The preparation method according to claim 3, characterized in that, The reduction is carried out in a hydrogen-containing mixed atmosphere, wherein the volume concentration of hydrogen in the mixed atmosphere is 5-20%.

6. The application of the esterification hydrogenation composite catalyst according to claim 1 or 2 or the esterification hydrogenation composite catalyst obtained by the preparation method according to any one of claims 3 to 5 in the hydrogenation synthesis of long-chain alcohols.

7. A method for preparing bio-based nonylene glycol and bio-based nonylene glycol, characterized in that, Includes the following steps: (1) Oleic acid, oxidant, first catalyst and organic solvent are mixed and subjected to first oxidation reaction to obtain oleic acid ozonide; (2) The oleic acid ozonide is subjected to a second oxidation reaction under the second catalyst to obtain a mixture of nonanoic acid and azelaic acid; (3) The mixture of nonanoic acid and azelaic acid and methanol were subjected to esterification reaction under the condition of a third catalyst to obtain methyl nonanoate and dimethyl azelaate; (4) Under the conditions of esterification and hydrogenation composite catalyst, methyl nonanoate and dimethyl azelate are hydrogenated to obtain bio-based nonadiol and bio-based nonanol. The esterification hydrogenation composite catalyst is the esterification hydrogenation composite catalyst according to claim 1 or 2, or the esterification hydrogenation composite catalyst obtained by the preparation method according to any one of claims 3 to 5.

8. The preparation method according to claim 7, characterized in that, The first catalyst is MnO2; the temperature of the first oxidation reaction is -10~80℃, and the time of the first oxidation reaction is 80~240min.

9. The preparation method according to claim 7, characterized in that, The temperature of the second oxidation reaction is 50~130℃, and the reaction time is 60~400min.